Received 14 May 2004; received in revised form 12 November 2004; accepted 15 November 2004
Available online 16 March 2005
Abstract
Many scientific papers have been written concerning gas sensors for different sensor applications using several sensing principles. This
review focuses on sensors and sensor systems for gaseous ammonia. Apart from its natural origin, there are many sources of ammonia,
like the chemical industry or intensive life-stock. The survey that we present here treats different application areas for ammonia sensors
or measurement systems and different techniques available for making selective ammonia sensing devices. When very low concentra-
tions are to be measured, e.g. less than 2 ppb for environmental monitoring and 50 ppb for diagnostic breath analysis, solid-state ammonia
sensors are not sensitive enough. In addition, they lack the required selectivity to other gasses that are often available in much higher
concentrations. Optical methods that make use of lasers are often expensive and large. Indirect measurement principles have been de-
scribed in literature that seems very suited as ammonia sensing devices. Such systems are suited for miniaturization and integration to make
them suitable for measuring in the small gas volumes that are normally available in medical applications like diagnostic breath analysis
equipment.
© 2005 Elsevier B.V. All rights reserved.
1. Introduction vices [9] or gas sensor arrays used in electronic noses [4,10].
The review presented here will focus on one specific gas,
Thousands of articles have been published that deal with ammonia.
some sort of gas sensor. This makes it virtually impossible to After a brief introduction of the origin of ammonia in
write a review article, completely covering this area. When the earth’s atmosphere, we consider various artificial sources
looking in the scientific literature, summarizing articles can of ammonia in the air, such as intensive life-stock with
be found that deal with specific application areas or specific the decomposition process of manure, or the chemical in-
types of gas sensors. Examples of review articles about ap- dustry for the production of fertilizers and for refrigera-
plications for gas sensors are: high volume control of com- tion systems. Subsequently, different application areas for
bustibles in the chemical industry [1], exhaust gas sensors for gaseous ammonia analyzers are investigated with a sum-
emission control in automotive applications [2,3] or monitor- mary of the ammonia concentration levels of interest to
ing of dairy products for the food industry [4]. Articles that these different areas. Applications in the agricultural and
emphasize a specific type of gas sensor are written about, for industrial chemistry areas are discussed, as well as envi-
example, solid state gas sensors [5], conducting polymer gas ronmental, automotive and medical applications for ammo-
sensors using e.g. polyaniline [6], mixed oxide gas sensors nia sensing devices. The overview of application areas pro-
[7], amperometric gas sensors [8], catalytic field-effect de- vides us with an indication of the required specifications,
like detection limits and response time, which will be used
∗Corresponding author. Tel.: +31 53 489 2755; fax: +31 53 489 2287.
as a guideline for the consideration of different measur-
E-mail address: b.h.timmer@el.utwente.nl (B. Timmer). ing principles and techniques, as discussed in the next sec-
URL: http://www.bios.el.utwente.nl. tion.
0925-4005/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2004.11.054
B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677 667
There are numerous smaller sources of ammonia, e.g. sur- Furthermore, exposure to high ammonia concentrations is
face water. Normally seas and oceans act as a sink for ammo- a serious health threat. Concentration levels near intensive
nia but occasionally they act as an ammonia source [22,23]. farming can be higher than the allowed exposure limit. This
Ammonia is produced because of the existence of ammonium results in unhealthy situations for farmers and animals inside
ions that are transformed to gaseous ammonia by alkaline the stables, where the concentrations are highest.
rainwater [23]. Another interesting point is the formation of ammonium
salt aerosols. Sulphuric acid and nitric acid react in the at-
mosphere with ammonia to form ammonium sulphate and
3. Application areas of ammonia sensors
ammonium nitrate [25]. These salts are condensation nuclei,
forming several nanometre sized airborne particles. There-
There are many ways to detect ammonia. High concentra-
fore, ammonia reduces the quantity of acids in the atmo-
tions are easy to detect because the gas has a very penetrat-
sphere. These ammonia aerosols have a sun-blocking func-
ing odour. With respect to other odorous gasses, the human
tion, as can often be seen above large cities or industrial areas,
nose is very sensitive to ammonia. To quantify the ammonia
as shown in Fig. 3. These clouds of smog have a temperature
concentration or determine lower concentrations of ammo-
reducing effect. This effect however, is presently hardly no-
nia, the human nose fails. However, in many occasions, the
ticeable due to the more intense global warming caused by
ammonia concentration has to be known, even at ultra low
the greenhouse effect.
concentrations of less than parts per billion in air (ppb) [24].
Ammonia levels in the natural atmosphere can be very
This section focuses on four major areas that are of inter-
low, down to sub-ppb concentration levels above the oceans.
est for measuring ammonia concentrations; environmental,
The average ambient ammonia concentration in the Nether-
automotive, chemical industry and medical diagnostics, and
lands is about 1.9 ppb. Very accurate ammonia detectors with
describes why there is a need to know the ammonia con-
a detection limit of 1 ppb or lower are required for measuring
centration in these fields. Where possible the concentration
such concentrations. Near intensive farming areas, ammo-
levels of interest are given for the different application areas.
nia concentrations are much higher, up to more than 10 ppm
3.1. Environmental gas analysis [26]. It depends on the actual application what concentration
levels are of interest. This also determines the time resolu-
The smell of ammonia near intensive farming areas or tion of the required analysis equipment. Monitoring ambient
when manure is distributed over farmland is very unpleasant. ammonia levels for environmental analysis does not demand
B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677 669
The automotive industry is interested in measuring atmo- The major method for chemically producing ammonia is
spheric pollution for three reasons [27]. First, exhaust gasses the Haber process. The German scientist Fritz Haber started
are monitored because they form the major part of gaseous working on a way to produce ammonia in 1904 [33]. In
pollution in urban sites. For instance, ammonia exhaust is 1918 he won the Nobel Prize in Chemistry for his inven-
associated with secondary airborne particulate matter, like tion. Ammonia is synthesized from nitrogen and hydrogen
ammonium nitrate and ammonium sulphate aerosols, as dis- at an elevated temperature of about 500 ◦ C and a pressure
cussed in the previous section. Ammonium aerosols are mea- of about 300 kPa using a porous metal catalyst. The process
sured to be up to 17% of the particulate matter concentration was scaled up to industrial proportions by Carl Bosch. The
smaller than 2.5 m [27]. Ammonia emissions have been process is therefore often referred to as the Haber–Bosch
measured up to 20 mg/s or up to 8 ppm ammonia in exhaust process.
gas [28,29]. Ammonia production was initiated by the demand for an
A second reason for the automotive industry to be inter- inexpensive supply of nitrogen for the production of nitric
ested in detectors for atmospheric pollution like ammonia, is acid, a key component of explosives. Today, the majority
air quality control in the passenger compartment [27]. Mod- of all man made ammonia is used for fertilizers or chemical
ern cars are frequently equipped with an air conditioning sys- production. These fertilizers contain ammonium salts and are
tem. This system controls the temperature and the humidity used in the agricultural sector.
of the air inside the car. Fresh air can be taken from the outside Another substantial part is used for refrigeration. Ammo-
of the car or it can be created by conditioning and circulat- nia was among the first refrigerants used in mechanical sys-
ing air inside the car. When there is low quality air outside tems. Almost all refrigeration facilities used for food pro-
the car, like air with smoke near a fire or a factory, the sys- cessing make use of ammonia because it has the ability to
tem should not take up new air from outside. A major source cool below 0 ◦ C [34,35]. The first practical refrigerating ma-
of unpleasant smell is the smell of manure near farms and chine was developed in 1834 and commercialised in 1860.
meadows. This smell is caused by the increased ammonia It used vapour compression as the working principle. The
concentration in these areas. For indoor air quality monitors, basic principle: a closed cycle of evaporation, compression,
the detection limit should lie around the smell detection limit condensation and expansion, is still in use today [36].
of about 50 ppm. Moreover, for such an application it is im- Because the chemical industry, fertilizer factories and re-
portant that the sensor responds very fast. The air inlet valve frigeration systems make use of almost pure ammonia, a leak
should be closed before low-quality gas is allowed into the in the system can result in life-threatening situations. All fa-
car. A response time in the order of seconds is required. cilities using ammonia should have an alarm system detect-
A third application for ammonia sensors in the automotive ing and warning for dangerous ammonia concentrations. The
area is NOx reduction in diesel engines. Modern diesel en- maximum allowed workspace ammonia level is tabulated to
gines operate at high air-to-fuel ratios that result in an excess be 20 ppm. This is a long-term maximum and no fast detec-
of oxygen in the exhaust gas, resulting in large concentrations tors are required, a response time in the order of minutes is
of NO and NO2 (NOx ) [30,31]. Toxic NOx concentrations are sufficient. Especially in ammonia production plants, where
lowered significantly by selective catalytic reduction (SCR) ammonia is produced, detectors should be able to withstand
670 B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677
Table 1
Requirements for ammonia analysis equipment in different application areas
Application Detection limit Required Temperature Remarks
response range
time
Environmental
Monitoring ambient conditions 0.1 ppb to >200 ppm [24] Minutes 0–40 ◦ C Reduce environmental pollution
Measure in stables 1 to >25 ppm [26] ∼1 min 10–40 ◦ C Protect livestock animals and farmers
Automotive
Measure NH3 emission from vehicles 4–>2000 g/min [28] Seconds Up to 300 ◦ C NH3 emission is not regulated at this time
(concentration unknown)
Passenger cabinet air control 50 ppm [37] ∼1 s 0–40 ◦ C Automotive air quality sensor mainly aim
on NOx and CO levels [26]
Detect ammonia slip 1–100 ppm [29] Seconds Up to 600 ◦ C Control Urea injection in SCR NOx
reduction
Chemical
Leakage alarm 20–>1000 ppm [37,40] Minutes Up to 500 ◦ C Concentrations can be very high at NH3
plants and can even be explosive
Medical
Breath analysis 50–2000 ppb [42,46] ∼1 min 20–40 ◦ C Diagnosis of peptic ulcer cause by
bacteria, small gas volumes
in the air. The expired ammonia levels increase exponential done on these types of gas sensors [7,49–53], especially in
with the workload. The concentration levels of interest, when Japan [54]. These sensors are rugged and inexpensive and
measuring expired ammonia, are in the range of 0.1 to 10 ppm thus very promising for developing gas sensors. Many models
[38]. have been proposed that try to explain the functionality of
these types of sensors [50]. It is well established by now
3.5. Summary of application areas that the gas sensors operate on the principle of conductance
change due to chemisorption of gas molecules to the sensing
The application areas that have been discussed in this sec- layer.
tion are summarized in Table 1. The lower ammonia concen- A common model is based on the fact that metal-oxide
tration that is of interest is given as the required lower de- films consist of a large number of grains, contacting at their
tection limit. Estimations are given for the required response boundaries [51]. The electrical behaviour is governed by the
time and operation temperature. formation of double Schottky potential barriers at the inter-
face of adjacent grains, caused by charge trapping at the inter-
face. The height of this barrier determines the conductance.
4. Ammonia sensing principles When exposed to a chemically reducing gas, like ammonia,
co-adsorption and mutual interaction between the gas and the
There are many principles for measuring ammonia de- oxygen result in oxidation of the gas at the surface. The re-
scribed in literature. A different sensor is used in the exhaust moval of oxygen from the grain surface results in a decrease
pipe of automobiles than for measuring ultra-low concen- in barrier height [52]. The energy band diagram at the grain
trations of ambient ammonia for environmental monitoring. boundaries is shown in Fig. 6.
The most frequently used techniques in commercial ammo- As can be concluded from this model, metal-oxide sensors
nia detectors are discussed in this section. First, metal-oxide are not selective to one particular gas. This is a major draw-
gas sensors are described. Secondly, catalytic ammonia de- back. Different approaches to make selective sensor systems
tectors are dealt with, followed by conducting polymer am- have been applied [55], like principle component analysis
monia analyzers and optical ammonia detection techniques. [56], artificial neural networks, also known as the artificial
In the fifth sub-section, indirect systems using gas samplers nose [4,10,57] or conductance scanning at a periodically var-
and specific chemical reactions to make a selective ammo- ied temperature [58]. Varying the temperature changes the
nia analyzer are discussed, followed by a summary of the current density through a Schottky barrier but chemisorption
described techniques. is also a function of the temperature. It is shown that these
two effects have a different temperature dependency for dif-
4.1. Metal-oxide gas sensors ferent gasses. Techniques have been shown to create micro-
machined isolated hotplates that can be used to miniaturize
The ammonia sensors that have been manufactured in the and integrate these types of sensors on a chip [59–61].
largest quantities are without doubt metal-oxide gas sensors, A different approach to make selective metal-oxide gas
mostly based on SnO2 sensors [7]. A lot of research has been sensors is by using metals or additives that enhance the
672 B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677
Fig. 6. Energy band diagram showing the Schottky barrier height at the grain boundary of tin oxide without and with a chemically reducing gas [51].
chemisorption of specific gasses. WO3 based sensing ma- tection limits. Normal detection limits of these sensors range
terial is demonstrated to respond to NH3 and NO [62,63]. from 1 to 1000 ppm [63,66]. These sensors are commercial
Many materials have been added to this sensing material in available and are mainly used in combustion gas detectors
order to enhance the sensitivity and the selectivity towards [67] or gas alarm systems, for instance for reliable ammo-
these two gasses. The response to the two gasses can be ad- nia leakage detection in refrigeration systems [58]. First air
justed, as is shown in Fig. 7. Known additives for optimising quality monitoring systems for regulating ventilation into the
the ammonia sensitivity of SnO2 based ammonia sensors are passenger compartment in cars are being implemented.
Pd, Bi and AlSiO3 [64] or Pt and SiO2 [65].
The lowest ammonia detection limit found in literature is 4.2. Catalytic ammonia sensors
1 ppm, using a WO3 ammonia sensor with Au and MoO3
additives. The sensor is operated at an elevated temperature A great number of papers are published about reactivity of
of more than 400 ◦ C [63]. Most sensors have even higher de- catalytic metals to specific gases, for instance ammonia, hy-
Fig. 7. Sensitivity adjustment of a WO3 metal-oxide gas sensor to NH3 and NO at 350 ◦ C with 1 wt.% additives [62].
B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677 673
drogen, carbon monoxide or organic vapours [9,68,69]. The change in colour when ammonia reacts with a reagent. With
charge carrier concentration in the catalytic metal is altered the second principle optical absorption detection is applied
by a change in concentration of the gas of influence. This as a method to sense gasses.
change in charge carriers can be quantified using a field effect
device, like a capacitor or a transistor [70,71]. The selectivity 4.4.1. Spectrophotometric ammonia detection
of these sensors depends on parameters like the used catalytic Spectrophotometry is a technique where a specific reac-
metal, the morphology of the metal layer and the operating tion causes a coloration of an analyte. The best known exam-
temperature. Ammonia field effect transistors, gasfets, using ple is pH paper. A piece of this paper in a solution colorizes
a palladium gate material have been shown, resulting in a according to the pH of the solution. There are many com-
detection limit of 1 ppm. mercially available detection kits for all kinds of ions and
The catalytic reaction of a metal layer with gaseous am- dissolved gasses.
monia can also be used in combination with a solid-state ion- There are different coloration reactions in use for dissolved
conducting material to form a gas-fuelled battery. These gas- ammonia. Best known is the Nessler reaction [80]. This am-
sensing systems are known as chemical cells. The catalytic monia detection method is readily available and applied fre-
reaction at the sensing electrode will cause a change in elec- quently for determining the total ammonia concentration in
trode potential. The resulting potential difference between the water, e.g. in aquaria where too high ammonia levels can
electrode and a counter electrode, over the conducting layer, cause fish to die. The Nessler reagent consists of dipotas-
is used to quantify the gas concentration. These sensors are sium tetraiodomercurate(II) in a dilute alkaline solution, nor-
commercially available for many different gasses. The lower mally sodium hydroxide. This reagent is toxic. There is not
detection limit is normally in the low-ppm range and the ac- much literature about quantitative measurements with this
curacy is limited. A chemical cell for ammonia is presented reaction [81], probably because of the disadvantages. Be-
in literature based on an anion-exchange membrane with a sides the toxicity, a second disadvantage is the formation of
Cu electrode and an Ag/AgCl counter electrode [72]. the non-soluble reaction product, a basic mercury(II) amido-
iodide [80], making the reaction difficult to implement in a
4.3. Conducting polymer gas detectors miniaturized detection system.
A second coloration method to measure ammonia con-
A third measurement principle for ammonia makes use centrations in aqueous solutions is the Berthelot reaction. A
of polymers. Different materials have been reported, like combination of ammonia, phenol and hypochlorite results in
polypyrrole [73] and polyaniline [6,74]. The sensing mech- a blue coloration [82,83]. This reaction uses less dangerous
anism of polypyrrole films is two-fold: first, there is an ir- chemicals and the reaction products are all soluble in water.
reversible reaction between ammonia and the polymer and, This makes it a suitable technique for integration in miniatur-
secondly, ammonia can reversibly reduce the oxidized form ized analysis systems [84]. One drawback of this technique is
of polypyrrole [75]. The reduction of the polymer film causes the rather slow kinetics of the reactions. This was improved
a change in the conductivity of the material, making it a suit- by miniaturization in a flow-through analysis system [85].
able material for resistometric [76] or amperometric ammo- The detection limit is about 5 M of ammonia in water or
nia detection [73]. Response times of about 4 min have been 90 ppb. This technique is still under development in order to
shown [74]. The irreversible reaction with ammonia results lower the detection limit [86].
in an increase in mass in the polymer film. Sensors have been To improve the sensitivity, the detection limit of the de-
described that detect ammonia using the change in frequency tector has to be improved. This is done by applying different
of a resonator, coated with ammonia sensitive polymer [77]. coloration principles, like thin layers of pH indicator [87],
However, the irreversible nature of the reaction causes the fluorescent materials that can be used to label ammonia [88]
sensitivity of the sensor to decrease over time when exposed or a combination of the two [89]. A second option is to apply
to ammonia [75]. Although regeneration mechanisms have a very sensitive detection principle, like a photon-counting
been proposed, this is a major drawback of this type of sensors optical sensor [89] or optical waveguide structures [87] to
[78]. Polyaniline proved to be a much more stable conducting quantify the coloration, resulting in very sensitive, ppt range,
polymer material. The polymer is believed to be deprotonated ammonia detectors.
by ammonia, which results in the change in conduction [79].
The lower detection limit of gas sensors based on the two 4.4.2. Optical absorption ammonia detection
described polymers is about 1 ppm [74,79]. These sensors Optical adsorption spectroscopy is used in the most sensi-
are commercially available for measuring ammonia levels in tive and selective ammonia detectors for ambient ammonia.
alarm systems. Systems with a detection limit of 1 ppb, that do a full mea-
surement in 1 s, have been reported [90] Such systems use a
4.4. Optical gas analyzers laser and a spectrograph. Light travels through air [91] or an
ammonia sensitive layer [92,93]. The spectrum of the light
There are two main optical principles for the detection reaching the detector is influenced by either the gas compo-
of ammonia described in literature. The first is based on a sition or the material characteristics as a function of the gas
674 B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677
composition. Fig. 8 shows an absorbance spectrogram found large volume of the analyte gas into a much smaller volume
in literature that clearly shows that ammonia can be distin- of liquid, where ammonium ions are formed [102]. Many
guished from interfering gasses, like CO2 and water vapour accurate ways to selectively measure low concentrations of
[94]. These systems are used in all kinds of gas analyzers in ammonium have been shown [24,98,99].
different application areas. Optical absorbance analyzers that
measure multiple gasses are commercially available but cost 4.6. Summary of detection principles
thousands of dollars.
Although very sensitive and selective ammonia detectors The ammonia detection principles that are discussed in this
are shown, there are some disadvantages when looking at section are summarized in Table 2. The best results found in
sensor systems for measuring in small volumes. First, the re- literature are given for the described detection principles.
quired equipment is very expensive. It has been tried to use
inexpensive diode-lasers to overcome this problem but this
also resulted in a decrease in sensitivity [95,96]. Secondly, the 5. Concluding remarks
sensitivity of absorption spectroscopy is partly determined by
the amount of gas between the light source and the detector. Now, the properties of the described sensors and sensor-
For a very accurate analysis the measurement system should systems can be compared with the demands of the described
be very large. Thus, miniaturization always results in an in- application areas, summarized in Table 2. The following con-
crease in the lower detection limit. Therefore, this principle clusions can be drawn:
is less suited for miniaturized ammonia sensors, e.g. breath
analyzers. • Environmental air monitoring systems require a detection
limit of less than 1 ppb. Some optical gas sensors are suit-
4.5. Indirect gas analyzers using non-selective detectors able and the indirect method has a sufficiently low detec-
tion limit [24,87,90,99]. However, the optical gas sensors
One major drawback of most available ammonia detec- are large and expensive, making them less suited. Also the
tion principles is the poor selectivity towards ammonia com- indirect method is rather large and the reagent consumption
pared to other gasses. However, it is possible to use a non- and maintenance requirements are demanding. A smaller
specific detection principle, like pH measurement or elec- system would be beneficial.
trolyte conductivity detection. In that case, the gas analysis • For measuring in stables, a lower detection limit of 1 ppm
system should comprise a selection mechanism that allows is required. All described sensor systems can be applied for
only the gas of interest to influence the medium surround- this purpose. Sensor equipment that requires much mainte-
ing the detector [24,97]. This can be accomplished by us- nance is inconvenient for farmers. For instance, conducting
ing gas diffusion separation with gas permeable membranes polymers seems less suited because regular regeneration
[24,97–99]. to prevent loss of sensitivity is required.
These types of air analysis systems make use of gas sam- • For automotive exhaust applications the required detec-
plers like denuders or diffusion scrubbers to sample ammonia tion limits are not very low, the described sensor systems
into a sample liquid [97,100,101]. A major advantage of us- are all sufficiently sensitive. The elevated temperature in
ing gas samplers in ammonia sensor systems is the fact that exhaust systems excludes fluidic systems and conducting
these systems pre-concentrate the ammonia by sampling a polymer sensors. Water would evaporate from the fluidic
B. Timmer et al. / Sensors and Actuators B 107 (2005) 666–677 675
Table 2
Parameters of different types of ammonia sensors and sensor systems
Principle Lower detection limit Response time Temperature range Remarks
Metal-oxide
WO3 1 ppm [63] ∼5 min 400 ◦ C Low selectivity drift
Catalytic metal
Palladium 1 ppm [70] ∼1 min Up to 600 ◦ C Low selectivity
Conducting polymer
Polyaniline 1 ppm [74,79] ∼3 min Up to 150 ◦ C (regeneration) Irreversible reactions
Optical gas sensors
Nessler 50 M (90 ppb) [85] ∼1 min 37 ◦ C For ammonia in water
Coulorometric 1 ppt [87] ∼5 min Expensive setup
Absorption spectroscopy 1 ppb [90] ∼5 min Large and expensive
Non-selective detectors
pH-transitions and EC detectors 100 ppt [24] ∼20 min 0–40 ◦ C Fluidic system
systems and conducting polymers need to be constantly re- [6] D. Nicolas-Debarnot, F. Poncin-Epaillard, Polyaniline as a new sen-
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